Method of treating textile materials



United States Patent 3,161,538 REETHOD 0F TREATING TEXTILE MATERIA Julian L. Azorlosa, Easton, Pa, and George G. Stoner,

Suffer-n, N.Y.,'assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed June 15, 1962, Ser. No. 262,693 7 Claims. (Cl. 117-4395) This invention relates to the treatment of yarns of natural or synthetic filamentary materials, and relates more particularly to a method of sizing such yarns. This application is a continuation-in-part of application Serial No. 662,571, filed May 31, 1957, now abandoned.

in converting yarn into fabric webs by weaving, knitting, knotting or other textile operations, it is customary to size the yarn, i.e., apply an adhesive coating thereto,

usually during the warping step, to impart strength to the yarn and to protect the yarn against damage during the said textile operations and during the handling of the fabric formed from the yarn. It has been common practice to employ starch solutions to size the yarn. Starch coatings, however, have a tendency to peel or powder off the yarn. Lately, many water-soluble synthetic materials have been used in the formation of sizing compositions, particularly for the sizing of snythetic polymer filamentary textile materials, such as nylon, poly-acrylonitrile and other hydrophobic yarns. Thus, one of such watersoluble synthetic material sizing compositions comprised an aqueous solution of polyacrylic acid (Acrysol A-1, Orthocryl 25, and Good-rite TS 200). -While this type of size exhibited the necessary adhesion to the polymer yarn to form a protective film thereon, the use thereof necessitated the exercise of great care lest the hands of the operative be injured because such sizes are strong acids. Moreover, such polyacrylic acid size causes severe corrosion of sizing equipment. Other sizes generally employed in the sizing compounds of synthetic yarns are certain Water-soluble resins such as, for example, a salt of styrene maleic anhydride copolymer, However, in order to dissolve such resin sizing materials a pH of 9 to 10 is required. Accordingly, the sizing solution formed is not completely satisfactory for use on cellulose ester textile materials such as yarns of cellulose acetate, cellulose propionate, cellulose butyrate and mixed esters thereof, or of regenerated cellulose textile materials such as viscose yarns, since too alkaline conditions havea harmful cf- 3,161,538 Patented Dec. 15,, 1964 wherein R represents methyl and ethyl, and (2) an alcohol selected from the group consisting of methanol, ethanol,

.- methoxyethanol, isopropanol and n-propanol, the cation of said salt being selected from the group consisting of sodium, potassium and ammonium.

Examples of the partial esters of vinyl ether-maleic anhydride copolymers employed in accordance with our in vention are:

' Half methyl ester of vinyl methyl eth'er-maleic anhydride feet on such cellulosic materials, i.e., they cause a frosty a partial ester of a vinyl-maleic .anhydride copolymer whereby the textile characteristics of said filaments are improved.

pear from the following: detailed description and claims.

We have found that the handling and processing of textile materials containing synthetic hydrophobic filaments having a basis of a polyamide, polyacrylonitrile, polyester, or polyvinyl halide, as well as textile materials containing synthetic hydrophilic filaments having a basis of a cellulose ester or regenerated cellulose and textile material having a basis of protein, cotton, linen or other natural materials, may be greatly improved by treating said textile materialswith solutions of alkali salts of partial esters,

. copolymer Half ethyl ester of vinyl methyl ether-maleic anhydride copolymer Half n-propylester of Vinyl methyl ether-maleic anhydride copolymer 1 Half isopropyl ester of vinyl methyl ether-maleic anhydn'de copolymer Half methyl ester of vinyl ethyl ether-maleic anhydride copolymer Half ethyl ester of vinyl copolymer Half methoxyethyl ester of vinyl methyl ether-maleic anhydride copolymer Half methoxyethyl ester of vinyl ethyl ether-maleic anhydride copolymer We have found that highly desirable results are obtained by applying to the textile materials the alkali or ammonitun salts of the foregoing partial esters, i.e., the sodium, potassium or ammonium salts thereof. All of the said partial esters of the vinyl ether-maleic anhydride copolymers as their sodium, potassium and ammonium salts make valuablesizing compositions since they are water-soluble at a pH of 8 or less and do not require the high p-l-I condition necessary for the solubilizing of other resin sizes. Accordingly, the relatively low pH sizing solutions formed therefrom do not adversely affect textile materials having a basis of cellulose ester, a regenerated cellulose, or a vinyl polymer.

The sizing composition is applied to the yarns in the form of a solution prepared by dissolving the partial ethyl ether-maleic anhydride .ester of the vinyl ether-maleic anhydride copolymer in warm water and mixing therewith an inorganic base, such as sodium hydroxide, potassium hydroxide or ammonium hydroxide, or an organic base, such as triethanolamine Other objects and advantages of this invention will ap or the like, in an amount sufficient to form a sizing solution having a pH no greater than 8. The sizing solution may be applied to the above-specified natural or synthetic yarns for example by passing a warp of said yarns through a dip tank containing said sizing solution and then through squeeze rolls to remove the excess and finally over one to seven steam heated cans for drying. The temperatureof the c'ans is maintained at about C. The

I amount of size applied to the yarn is preferablyon the order of from 1 to 107%. on the weight of the yarn.

The salts of the partial esters of the vinyl ether-maleic anhydride copolymers may be preformed in any suitable manner and may be added in this form in order to prepare the aqueous solutions of this invention.

The following examples serve to illustrate our invention but are not 'to be considered as limitative.

i xample I 188 parts by weight of the half methyl ester of the vinyl 3,1 1% methyl ether-maleic anhydride is dissolved in 2000 parts by weight of water containing 35 parts NaOH at a temperature of 40 C. and the pH adjusted to 7.0 with NaQl-I.

A film of the above clear, colorless, free-flowing solution is cast on a-sheet of cellulose acetate and is dried for five minutes at 80 C. at a forced-draft oven. The dried film is flexible, has good adhesion to the surface of the cellulose acetate and is easily removed by water. There is no change in the surface appearance of the cellulose acetate sheet.

Example 11 202 parts by weight of the half ethyl ester of vinyl methyl ether-maleic anhydride copolymer and 35 parts by weight of NaOH added generally to 2000 parts by weight of water at a temperature of 150 F. and the mixture agitated for two or more hours. The pH of the resultant solution is adjusted to 7 by addition of NaOH.

A film of the above clear, colorless free-flowing solution of the sodium salt of the half ester of vinyl methyl etheranaleie anhydride is cast on a sheet of cellulose acetate and is dried for five minutes at 80 C., in a forceddraft oven. The dried film is flexible, has good adhesion to the surface of the cellulose acetate and is readily removed by water.

There is no change in the surface appearance of the cellulose acetate sheet. I

Example 111 A film of the solution mentioned above in Example 2 is cast on a polyacry-lonitrile surface (produced by casting a solution of polyacrylonitrile in butyrolactone on a glass plate and drying toconstant weight) and dried for five minutes at 80 C. in a forced-draft oven- The dried film is flexible, has good adhesion to the surface of the polyacrylonitrile, and is readily removed by water.

Example IV A slashing trial was carried out with the half ethyl ester of vinyl methyl ether-maleic anhydride copolymer using plant scale equipment. Thirty pounds of the half ester was dissolved slowly with agitation at 140 F. in a 250 gallon size kettle containing 100 gallons of water and 10. pounds of 50% aqueous NaOI-I. The pH was adjusted to 7 with 50% aqueous NaOH.

The prepared size solution was run into the size box of a seven can Johnson Slasher. Approximately 120 yards of an all-acetate warp were run through the half ethyl ester solution at a speed of 30 yards per minute. Processing was normal with no sticking to the cans and no shedding at lease rods.

The sized warp was woven up into a 110 yard cut of an 180/60, 46" acetate taffeta. Again processing was eases normal with no evidence of shedding or excessive endsdown during weaving.

Performance of the half ethyl ester at 30 pounds/100 gallons was considered equal in performance to a conven- Having described our invention, what we desire to secure by Letters Patent is:

1. A method of treating a yarn formed of a material selected from the group consisting of natural and synthetic filamentary materials which comprises, preliminary to fashioning said yarn into a fabric, sizing the surfaces of said yarn by applying thereto an aqueous solution of an alkali salt of a partial ester of a vinyl lower allryl ethermaleic anhydride copolymer, said partial ester being about a half ester of (1) said vinyl lower alkyl-maleic anhydride copolymer and (2) an alcohol selected from the group consisting of methanol, ethanol, methoxyethanol, isopropanol, and n-propanol, said solution having a pH of at most 8, said solutions being applied in an amount sulficient to deposit from about 1% to about 10% by weight, based on the weight of said yarn, of said salt of said ester of said copolymer on the surface of said yarn upon the removal of water from said solution, and then drying said treated yarn.

2. A method of treating a' yarn formed of a material selected from the group consisting of natural and synthetic materials comprising, preliminary to fashioning said yarn into a fabric, sizing the surfaces of said yarns by applying an aqueous solution of a salt of a half ester of (1) a copolymer of maleic anhydride and a vinyl ether having the formula:

CH =CHOR wherein R is a member of the group consisting of methyl and ethyl and (2) an alcohol selected from the group consisting of methanol, ethanol, methoxyethanol, isopropanel and n-propanol, the cation of said salt being selected rom the group consisting of sodium, potassium and ammonium, said solution having a pH of at most 8, said solution being applied in an amount sutficient to deposit from about 1% to about 10% by weight, based on the weight of the yarn, of said copolymer on the surface of said yarn and then drying said treated yarn to provide a yarn ready for weaving.

3. The method in accordance with claim 2 wherein said salt of said ester of said copolymer is a sodium salt of a half methyl ester of a vinyl methyl ethenmaleic anhydride copolymer.

4. The method in accordance with claim 2 wherein said salt of said ester of said copolymer is a sodium salt of a half ethyl ester of a vinyl methyl ether-maleic anhydride copolymer.

5. The method in accordance with claim 2 wherein said salt of said ester of said copolymer is a sodium salt of a half methyl ester of a vinyl ethyl ether-maleic anhydride copolymer.

6. The method in accordance with claim 2 wherein said salt of said ester of said copolymer is a sodium salt of a half methoxyethyl ester of a vinyl methyl ether-maleic anhydride copolymer.

7. The method in accordance with claim 2 wherein said salt of said ester of said copolymer is a sodium salt of a half propyl ester of a vinyl methyl ether-maleic anhydride copolymer.

References Cited in the file of this patent UNITED STATES PATENTS Rossin et al. Aug. 10, 1954 

1. A METHOD OF TREATING A YARN FORMED OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF NATURAL AND SYNTHETIC FILAMENTARY MATERIALS WHICH COMPRISES, PRELIMINARY TO FASHIONING SAID YARN INTO A FABRIC, SIZING THE SURFACES OF SAID YARN BY APPLYING THERETO AN AQUEOUS SOLUTION OF AN ALKALI SALT OF A PARTIAL ESTER OF A VINYL LOWER ALKYL ETHERMALEIC ANHYDRIDE COPOLYMER, SAID PARTIAL ESTER BEING ABOUT A HALF ESTER OF (1) SAID VINYL LOWER ALKYL-MALEIC ANHYDRIDE COPOLYMER AND (2) AN ALCOHOL SELECTED FROM THE GROUP CONSISTING OF METHANOL, ETHANOL, METHBOXYETHANOL, ISOPROPANOL, AND N-PROPANOL, SAID SOLUTION HAVING A PH OF AT MOST 8, SAID SOLUTION BEING APPLIED IN AN AMOUNT SUFFCIENT TO DEPOSIT FROM ABOUT 1% TO ABOUT 10% BY WEIGHT, BASED ON THE WEIGHT OF SAID YARN, OF SAID SALT OF SAID ESTER OF SAID COPOLYMR ON THE SURFACE OF SAID YARN UPON THE REMOVAL OF WATER FROM SAID SOLUTION, AND THEN DRYING SAID TREATED YARN. 